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Issue 30, 2011
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Peroxy radical isomerization in the oxidation of isoprene

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We report experimental evidence for the formation of C5-hydroperoxyaldehydes (HPALDs) from 1,6-H-shift isomerizations in peroxy radicals formed from the hydroxyl radical (OH) oxidation of 2-methyl-1,3-butadiene (isoprene). At 295 K, the isomerization rate of isoprene peroxy radicals Image ID:c1cp21330j-t1.gif relative to the rate of reaction of Image ID:c1cp21330j-t2.gif is Image ID:c1cp21330j-t3.gif, or k295isom ≃ 0.002 s−1. The temperature dependence of this rate was determined through experiments conducted at 295, 310 and 318 K and is well described by Image ID:c1cp21330j-t4.gif. The overall uncertainty in the isomerization rate (relative to Image ID:c1cp21330j-t5.gif) is estimated to be 50%. Peroxy radicals from the oxidation of the fully deuterated isoprene analog isomerize at a rate ∼15 times slower than non-deuterated isoprene. The fraction of isoprene peroxy radicals reacting by 1,6-H-shift isomerization is estimated to be 8–11% globally, with values up to 20% in tropical regions.

Graphical abstract: Peroxy radical isomerization in the oxidation of isoprene

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26 Apr 2011
08 Jun 2011
First published
24 Jun 2011

Phys. Chem. Chem. Phys., 2011,13, 13607-13613
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Peroxy radical isomerization in the oxidation of isoprene

J. D. Crounse, F. Paulot, H. G. Kjaergaard and P. O. Wennberg, Phys. Chem. Chem. Phys., 2011, 13, 13607
DOI: 10.1039/C1CP21330J

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